Polymerization process



United States Patent POLYMERIZATION PROCESS Arthur William Anderson and Manville Isager Bro, Wilmington, Del., assignors to E. I. du Pont'de, Ne-

mours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Application February 1, 1955 Serial No. 485,616

12 Claims. Cl. 260-949) in the presence of catalysts which are capable of yielding. I,

free radicals under polymerization conditions. Recently a novel polymerization catalyst had been described in copending application S. N. 450,243, filed August 16, 1954, in which a reduced titanium metal complex is disclosed as a catalyst which produces extremely high molecular weight, substantially unbranched polymers and copolymers of ethylene. This active titanium complex is formed by reducing a tetravalent or trivalent titanium salt or ester to a valence state below three, and combining the reduced product with an ethylenically unsaturated hydrocarbon. The initiator thus formed is efiective for the polymerization of said unsaturated hydrocarbon to high molecular weights. This type of catalyst has been called a coordination catalyst, because it is believed that the reduced titanium will coordinate with the ethylenically unsaturated compound and cause polymerization, The reduction of the tetraor trivalent titanium to a valence state below three is accomplished by strong: re-': ducing agents such as metallo-organic compounds, metal hydrides, Grignard reagents and metals such as'zinc and; metals above zinc in the electromotive" series; The polymers obtained by this type of polymerization are' characterized by their linear structure. The linear poly ethylene thus obtained has virtually no side branches such as methyl substitution and a very small number 'of ill-r nylidenegroups. Polyethylenes obtained by this method" have extremely high molecular weights and usually'arel of higher density than polymers made by well-known free radical polymerization processes. The fact that the co-, ordination initiator system gives rise to a type of polymer which differs fromythat obtained by the previously known free radical polymerization system can be explained by the theory, which as yet has not been completely established and verified, that the titanium when reduced to a.

valence state below three reacts with ethylene to ,form

a chain generating nucleuswhich is capable of combining continuously with ethylene monomer units' which enter between the nucleus and the growing chain. In contrast withthis, in the previously known free radical polymeri-" zation the initiating free radical remains at the inactive end of the growing polymeric chain. The coordination initiator system has been found to be useful over a'wide range of temperature and pressure, and'is, therefore, a highly valuable system for polymerizing ethylene. Q

As stated hereinabove, metals in the electromotivel series which are above zinc, such as alkali metals, are reducing agents for titanium, capable of reducingtitanium from a valence state above three to one below three. The'r'eaction mechanism by which this reduction occurs has at the present time notbeen' established. In comparison with other reducing agents useful in the reduction V ofv titanium, the alkali metals were found to be less active than certain other reducing agents such as metalloorganic compoundsye. g. lithium aluminum. alkyls. Because of their availability, low cost and stability, as compared withfthe metallo-organic derivatives, alkali metals would be a preferred reducing agent in polymerization systems using coordination initiators if methods could be found for increasing the activity of such systems. It is, therefore, one of the objectives of this invention to increasethe reactivity of coordination initiator systems using alkali metals as reducing agents. Affurther object is "to provide highly reactive initiator systemsfor the polymerization of ethylene to high molecular weight polymers. Another object of this invention is to provide an improved polymerization system using 'a coordination initiator. Further objects will become apparent hereinafter. I l It hasnow been discovered that the addition of small quantities of iacetylenic hydrocarbons and substituted ethylenically unsaturated hydrocarbon to coordination H initiator systems employing alkali metals as reducing agents give asurprising increase in the reactivity of the initiators when used in the polymerizatio'nand copolymerizatio'n of ethylene to high molecular weight solid polymers. The invention is described mainly with regard to titanium coordination initiators, which,.although prefe'rred, are'not' the only coordination initiators useful in the present invention. Other metals useful in coordination initiators are'described hereinbelow in greater detail.

Thereason for this surprising increase of reactivity of' the initiator' system by the addition of compounds of the class stated hereinabove is not known, although it is believed that'the activators aid in the reduction of the titanium to a valence state of below three. In the absence of sodium, no solid polymer is formed. Furthermore,

, no substantial polymerization of ethylene occurs in the compounds, because of their greatest elfect on the titanium absence of the tetravalent titanium halide. In the absence ofthe activator, the polymerization of ethylene is sluggish. In the presence of all three components, however, a" highly reactive initiator system is formed. Possibly the improved activity is due to a reaction of the alkali metal with the activator in the presence of the tetraor trivalent titanium salt, such as titanium tetrachloride,

this intermediate thenreacts with the titanium compound forming an unstable titanium alkyl (or alkenyl) tri-,

chloride or titanium alkyl (or alkenyl) dichloride,'or some related structure; such structuresmay decompose rapidly, reducing the titanium to a valence state below three, whereupon the titanium can coordinate with ethylene and cause the polymerization to proceed.- The, re-

duction of the titanium ,to a valence state below three, although possible in the, presence of the alkali metal above, apparently becomes much easier when this titanium monoor dialkyl (or alkenyl) halide is formed with the activator. However, it should be realized that this is only one explanation of the facts and that others.

inventionis believed to aid in the reduction of the titanium. This tends to explain the extreme reactivity of initiator systems using acetylene in combination with an alkali metal. H

The activators used in the present invention, as described hereinabove, are hydrocarbons containing either.

a triple bond or a substituted double bond. The preferred amples but they are slightlyless active than theacetylenes.

Ethylene itself is not an effective activator forthe re Patented Mar. 24, 1959 for-"the caarainaasa" polymerization of ethylene in a titanium alkali-metal system includes the mono-, di-, tri-, or, tetra-substituted olefins. The substitution may consist of' alkyl radicals or aromatic radicals. Cyclic olefins such as cyclohexene are equally useful. erably',,.the allgyl radicals are those having from 1 to 10 carbon atoms. Oleiins, as well as, diolefins', such-as butadiene, may. be used to activate the. initiator system. Suitable examples includejpropylene, isobutylene, hexenes, styrene, decenes, etc.

In some instances, it was found that part of theactivator had copolymerized with the resulting ethylene polymer. This, can occur when an excess of the activator is present-during the reduction. Another explanation maybe that on, reduction of the titanium the activator is re-v stored. to its original structure.

The polymerization reaction is preferably carriedv out in. aninert liquid reaction medium such as a saturatedhy. dr'ocarbon or an aromatic hydrocarbon. Preferred re: action media. are benzene, toluene and cyclohexane. To achieve a rapid formation of the catalytically active; complex, it is preferred to employ solutions of the catalyst components: in the reaction medium. 'The activators, used in the presentinvention are generally miscible with the reaction media. The formation of the, active complex may be carriedoutprior, during or after the addition of; the monomer. titanium tetrahalide solution just prior to. the addition of the monomer by injection into the polymerization vessel containing a; solution of the other initiator components. The, pressure to be employed in. the polymerization using the alkali-metal-titanium initiator system may, be varied over a widerange from atmospheric pressure to very high. pressuresof 1,000 atmospheres and aboye generally; howe evenpressures from, 100 p.s.i. to 15,000 p.s.i. of ethylene are employed in order to facilitate the handling of ethyl;

Preffiled September 21, 1954. In general, it has been found that coordination catalysts can be formed with transition metals of groups H112 to VIb of the periodic table. The degree of catalytic activity may vary with each of these metals, the more active ones being the metals listed hereinabove. Thus, the term coordination catalyst is to be construed as, applying to the above-listed metals, which are capable of coordinating with ethylene and causing polymerization when. existing in a valence state below three. The activators used in the present process can also serve in an analogous manner in a coordination initiator system using a metal compound of the metals described .hereinabove, and sodium. as the reducing agent.

, merization media,

In general, it is preferred to add the,

cussed. avoi XPQllSlYQ QP FP Q SU qu pment... n

on ras ith. hst oor na i i. tiato y tems... h initiator system of; the present invention is most use ul; in a limited temperature range, It has been found that Polymerization rates decrease significantly as the reaction temperature. is increased to beyond 150 C. Evidently raising the temperature beyond 150 causes the initiatns italli m omplex. o c m s v r a tiveh ti r he reaction within the complex, possibly further reduction, detra from the ability. of the catalyst to polymerize ethylene to, a high molecular weight, polymer. At tern; peratures be'low 75 C., the polymerization rate is slow, Apparently it is necessary to.ha ve the alkali metal in a molten stage to cause the reaction of the sodium as,

bov s r b d-.' The p s r react cn. ems at teis e for ro nd. 1 0

n a lo ns, h l m ri at on. prams emes stimat on ita i m ompounds a ficien y solubl in. organic solvents to give the necessary concentration as a; catalyst may be employed generally. Of thesecompounds, the titanium tetrahalides are preferred, and more specifically titanium tetrachloride. Titanium compounds, such astitanium oxides, have not been found useful in the, present invention, The p rocess; of thisinventi'on has; r in h v s i s tib df srsnce to i aui. tjetrahalide as the catalyst component in which the titanium is reduced'to a, valence state below three. The ability of titanium to exist in such a valence state as to cause the polymerization of ethylene to solid polymersis not unique, buthas also been found in other metals suchas zirconium, vanadium, tungsten, molybdenum, niobium and tantalum. The catalytic activity of the above said metals, when reducedto avalence state below three,

has been described in the following copen'ding applications respectively: SLNi 450,268; filed August 16, 1954', SN. 455357, filed September 10, 1954; S.N. 453,145; e iAu u t 3. L ;,SN 3.14 .filsd sP-st 9 .4;

The. present invention is further illustrated by the fol lowingv examples Example lPolymerization of ethylene using propylene i as an activator Intoapressure reaction. vessel having a capacity of 3.30 ml. was charged 100 ml. of cyclohexane and 2.3 g. of sodium.(0.1 mol). The vessel was cooled and evacuated and;4.2.-fg. (0.1 mol). of propylene. was distilled in. The vessel, was. then heated to, 150 C. for 15 minutes after which, time. it was cooled. to room temperature. Into the. vessel. was then injected 3.46. g. (0.02 mol) ofv titaniumtetrachloride, dissolved. in 40 ml. of cyclohexane. The. reaction. vessel was heated to 100 C. and pressured with. ethylene to 5.00 to 70.0 psi. Maintaining thattemperature, the, reaction vessel was agitated for a period. of, 1 hour. The. ves'sel was then cooled, excess monomer was vented, off, and the resulting polymer was filtered from the reaction medium, washed and dried. 56.3 g. of a, solid white. polymer, was obtained. The polymer could be.

Example ll..Polymerizatz'onof ethylene using isobutylene as an activator To mlof cyclohexane .6 g.. offisobutylene (0..1'm.o1)- and.2 .3 g. of sodium (0.1 mol) were added. The resulting mixture was placed intoa pressure reaction vessel havinga capacity of 330ml. and heated to 150 C. for a,

period; of 15. minutes under autogenous, pressure. The.

reactionm-inture, was; cooled to 25 C. and thepolymerizai tion mixture wasflushed'with nitrogen and, evacuated. 3,.8, g.;. of. titanium: tetrachloride dissolved in. 4.0 ml. of. cyclo hexane y as- ,injected into thereaction mixture-and the reaction,vessel wasthen 'pressuredto 500 p.s.i. with ethylene andheatedto.a. temperature of C. for 1 hour under continuonsagitation. Atthe outset of the polymerization, the temperature-rose, to,15,0"C because of the exothermic. nature of. the reaction andpolymerization vessel had to be cooledto maintain the reactiontemperature of 105 C., After 1 hour, the reaction vessel wasv cooled to room. temperature, excess monomer gas vented'ofi, and the, resulting polymer was, filtered, washed and, dried. Approximately: 65. g, of awhite solid polymer was ob,

films by heating to 200 C. and pressing under 20,000 p.s.i. pressure for a period of2 minutes. The density of theresultnig polymer was found to be 0.943.. Infrared analysis indicated that no isobutylenehad copolymerized scribed hereinabove. In the absence of the activator under.

similar conditions, less than 1 g. of polymer was obtained.

Example XIV' with the ethylene. Using the procedure in Example II, 3.7 g. of titanium tetrabromide dissolved in 40 ml. of cyclohexane was ii" le usmg acetylene employed instead of the titanium tetrachloride. Upon as the washing and drying the polymer, 15 g. of a white solid. In a pressure reaction vessel having a capacity of 330 P y having dt-lllsity 0f W f m Th ml., 100 ml. of cyclohexane, 1.1 g. of sodium and 1.5 g. 10 P y could be l'llolded illto a tough, flexlble m by of acetylene were heated under autogenous pressure at t Piocedufe descrlbed heremaboye- 150 C. fol' a. period of minutes after the reaction vesh p o obtained y p y s y n wlth sel had been cooled, flushed with N and evacuated. The catalysts hereinabove disclosed are solid polymers exreaction mixture was cooled to room temperature and clusively and are not. contaminated with Friedel-Crafts 0.9 g. of titanium tetrachloride dissolved in 40 ml. of 15 typ of y p y The catalyst System O the p 'fi i. cyclohexane was injected into the reaction mixture. The ent invention is of extreme catalytic reactivity, and, reaction vessel was pressured to 500 p.s.i. with ethylene when emp y the more active activators S a a d h t d t 100 C, fo a er-ind f 1 h ur-unde con. ylene, great caution has to be exercised in preventing tinuous agitation. After 1 hour, the reaction vessel was a rapid rise in temperature during polymerization. Thus, cooled to room temperature, and the resulting polymer sufiicient cooling must be available to counteractthe was filtered, washed and dried. 39 g. of a solid polyrapid rise of temperature at the start of the polymerizeethylene was obtained. The polymer could be molded tion. i i v into tough, flexible films by'hea ting to 200 C. and press- 7 The quantity of the catalyst employed can be varied ing under 20,000 p.s.i. pressure. The density of the polyover a rather wide range. It is desirable to. employ a mer was found to be 0.968. catalyst concentration which is at least large enough to; E m L produce a reasonably rapid rate for areasonably long p period of time. Suitably, the preferred quantity is within Using the polymerization procedure described in the the range of 0.1 to 10% based on the weight of titanium, preceding examples, the activators listed in the table below perunit weight of monomer. The quantities of reducwere tested in the polymerization of ethylene as set forth ing agent and the activator are adjusted accordingly to in the table. the quantities of the titanium used A wide ratio of Activator Solvent Exam- Sodium, T1014, React. Pressure Yield, React. Film pleg. g. Ten p otEthy1-; g. Time, Proper- Density Remarks Type Arzlgoiint ene,p.s.l. Type cc. hour ties IV..- wmethyIsty- 6 2.3 3.8 100 500-700 cyclohexane- 100 1 '42 1 tough..- 0.9633 No activerene. torin polymer. v stilbene e 2.3 3.8 100 500-1,000 do 140 39 1 .do 0.94 Do. VI cis-butene-2..- 6 2.3 3.8 100 ,000 do 140 62 1 do- 0.94 VIL-.- cyclohexene-.- 100 ml.' 2.3 3.8 100 5001,000 33.5 1 .....do. 0.943 No cyclo- I hexane T 4 g in poly VIII-.. ethynyl ben- 2.3 3.8 100 5004.000 cyclohexane- 140 41.7 1 ..-do...'... I 0.943

tnii i liutene-z 6 2.3 3.8 100 BOO-1,000 -do 140 35.2 1 -do.. 0.34 x 'butadiene---- 5.4 2.3 3.8 100 coo-1,000 do 140 32 1 -do-- 0. 956

\ Example XI reducing agent andactivator may be employed- How Using the procedure in Example II, 3.8 g. of Zirconium ever, a preferred ratio of activatonand alkahrnetal to. tetrachloride dissolved in 40 ml. of cyclohexane was emi titamum ls molar who of actlvator alkah metai: ployedinstead of the solution of titanium tetrachloride. mamum leirahahde of A further decrease m Upon washing and drying the polymer 26 of a white the quanuties of the alkali metal and activator causes a solid polymer having a density of 0.948 was obtained. slgmficam decrease. In the f poiymenzatlfm of The polymer could be molded into tough flexible films ethylene. Substantially, 110 S1gnl fiC8. 1lt increase in the by the procedum described hereinabove rate of polymerization is noticed if either activator content or the quantity of the reducing agent is increased. Example XII The polymers which are made under the conditions Using the procedure described i Example 11 2 3 f hereinabove described frequently have such tremendously lithium and 6 g. of butene-l were dissolved in 100 ml. h1gh molecular Y that removal of catalyst by of cyclohexane instead of the sodium and the isobutylene. solving and filtefmg is extremely difficult- The best P Upon washing and drying the polym 55 of a hi cedure for obtaining the polymer in a clean form is to solid polymer having a density of 0.93 was obtained wash with acetone-hydrochloric acid mixture in a Waring The polymer could be molded i tough, flexibl fil by Blendor several times, followed by washing with acetone, the procedure described hereinabove In the absence f and thereafter, if necessary, followed by several acetonethe activator, 14 g. of a lower molecular weight polymer aqueous Sodium hydroxide Washfis, and finally y acetonewas b i under i1 di i water wash. Other methods of purifying the polymer Exam I XI" will occur to those skilled in the art.

p 8 Although the process of this invention has been de- Using the procedure described in Example II, 4 g. (0.1 scribed in reference to homopolymers of ethylene, it is mol) of potassium and 6 g. of butene-l were dissolved in to be understood that it equally well applies to the co 100 ml. of cyclohexane instead of the sodium and the isopolymerization of ethylene with comonomers such as butylene. Upon washing and drying the polymer, 9 g. of propylene and other ethylenically unsaturated monomers. a white, solid polymer was obtained. The polymer could It is quite possible that the comonomer used is at the be molded into tough, flexible films by the procedure desame time the activator for the catalyst system. As

T stated hereiuabove, excess quantities of the activator in noway"'affect thepolymeri'zationratesadversely.

The ethylene polymers obtained in accordance with the proeessof this invention are highly useful in numerous applications, especially inthe form"of* films, extruded articles; extruded insulation on Wire, fibersandfilament's, etc. In certain applications itmay be beneficial to retain the titanium in the polymer to impart greater heat stability to the polymer.

We' claim:

l. The process for preparing a homopolymer of ethylone which comprises contacting; ethylene-with a poly merization initiator in an inert, liquid hydrocarbon medium at' a temperature below 150 C., said initiator consisting essentially of the reaction product obtained o l-admixing a metal halide of the class consisting of titanium halides and zirconium halides; said halides being selected from the group consistingof' bromid'esr andchlorides; withan alkali meta'l and amember of the class "consisting of hydrocarbons having a triple bond between "carbon atoms and hydrocarbons of molecular weight higher than ethylene, having at least one nonbenzenoid ethylenic bond, said alkalimetal being present in suiiicient quantities to reduce themetal of said metal halide to a valence state below three and said hydrocarbon being present in at least equimolar quantities of said, alkali metal, and recovering a solid polymer of ethylene;

2: The process for preparing a homopolymer of'ethyl ene which comprises contacting ethylene with' a poly merization' initiatorin an inert, liquid hydrocarbon medium at a temperature below 150 C., said initiatorv consisting essentially of the reaction product obtained on admixing a titanium halide, saidhalide being selected from the group consisting of bromides and chlorides, with an alkali metal and a member of the class consisting, ofhydrocarbonshaving a triplebondbetween car-- bonatoms andhydrocarbons of molecular. weighthigher' than-ethylene having at least one non-benzenoid ethylenic bond;,said alkali metalbeing present in; sufiicient quantities to, reduce said titanium to a valence stateb'elow 7 organic solvent is cyclo'hexane.

three. and sai'd hydrocarbon being present in at least equimolarquantities of said alkali metal andrecovering a solidpolymenof ethylene.

3. The process of polymerizingethylene in an inert,

liquid hydrocarbon mcdiumtat a temperature 0575: to.

15.0 C., in. the presence. of. aninitiatorsystemconsisting essentially of the product formed by admixing titanium. tetrachloride with an alkali metal and a hydrocarbon havinga triple bond" between carbon atoms; said' alkali metal being present in sufiicient quantities to reduce said titanium to a valence state below three and said hydrocarbonbeingpresent inat leastiequimolar quantities of said 'alkalibmetal, and recovering a' solid polymer of ethylene.

4. The process as settforth in. claim 3 wherein the hydrocarbon component having a. triple bond between carbon atoms is acetylene.

5'. The process as set forth in claim 3 wherein the hydrocarbon component having a triple bond between carbon atoms is phenyl" acetylene.

6;. The process of polymerizing ethylene in an inert, liquid hydrocarbon medium'at a temperature of to' CL, in the presence of an initiatorsystem consisting essentially of theproduct formed by admixing titanium tetrachloride with arr'alkalimetal and a hydrocarbonha vingat least onenorr-benzenoid ethylenic' bond and" having at least threecarbon atoms, said alkali metal" beingjpresent in sufiicient quantity to reducesaid" titanium to a valence state below'three and said hydrocarbon being present in at l'easfe'quimolar' quantities of' said alkali metal, and recovering a solid polymer of ethylene;

7-;Theprocess as set forth in claim 6 wherein the hydrocarbon having an ethylenic double bond comprises ethylene substituted with one to three aromatic hydrocarbon radicals. 1

8. The process as set forth in claim 7 wherein the hydrocarbo'nis stilbene. v

9'; The process as set forth in claim 6 wherein the hydrocarbon comprises isobut'ylene.

10. The process as set forth in claim 6 wherein" the activator comprises. butadiene.

11.. The process of polymerizing ethylene which comprises adding to a-n' inert organic solvent at a temperature a of '75' to" 150 C., said' solvent. containing an initiator system consisting essentially of the product formed by admixing titanium tetrachloride; analkali metal; andacetylene in a molar weight ratio of 0.2/1t/ 1, and recover ing a solid polymer ofi ethylene.

12. A. process as set: forth in claim 11 wherein the-- References Cited in the tile of this patent UNIT ED STATES PATENTS 2691,1547 Field etal. OctQlQ, 1954' 2,700,663. Peters. Jan. 25, 1955 2,710,854 Seelig June 14, 1955 2,721,189 Andersonet a1;- Oct. 18, 1955 

1. THE PROCESS FOR PREPARING A HOMOPOLYMER OF ETHYLENE WHICH COMPRISES CONTACTING ETHYLENE WITH A POLYMERIZATION INITIATOR IN AN INERT, LIQUID HYDROCARBON MEDIUM AT A TEMPERATURE BELOW 150* C., SAID INITIATOR CONSISTING ESSENTIALLY OF THE REACTION PRODUCT OBTAINED ON ADMIXING A METAL HALIDE OF THE CLASS CONSISTING OF TITANIUM HALIDES AND ZIRCONIUM HALIDES, SAID HALDES BEING SELECTED FROM THE GROUP CONSISTING OF BROMIDES AND CHLORIDES, WITH AN ALKALI METAL AND A MEMBER OF THE CLASS CONSISTING OF HYDROCARBONS HAVING A TRIPLE BOND BETWEEN CARBON ATOMS AND HYDROCARBONS OF MOLECULAR WEIGHT HIGHER THAN ETHYLENE, HAVING AT LEAST ONE NONBENZENOID ETHYLENIC BOND, SAID ALKALI METAL BEING PRESENT IN SUFFICIENT QUANTITIES TO REDUCE THE METAL OF SAID METAL HALIDE TO A VALENCE STATE BELOW THREE AND SAID HYDROCARBON BEING PRESENT IN AT LEAST EQUIMOLAR QUANTITIES OF SAID ALKALI METAL, AND RECOVERING A SOLID POLYMER OF ETHYLENE. 